Secondary aliphatic amines containing tertiary carbon atoms



SECONDARY ALIPHATIC AMINES CONTAINING TERTIARY CARBON ATOMS Warren D.Niederhauser, Huntsville, -Ala., and Edward Broderick, Branford, Conn.,assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation ofDelaware No Drawing. Application January 29, 1957 Serial No. 636,849

16 Claims. 01. 260-583) This invention concerns secondary aliphaticamines and a method for their preparation. These amines arecharacterized by unique properties that make them valuable in manyhydrometallurgical applications for separating metals from aqueoussolutions of their salts and for extracting mineral acids from aqueoussystems.

The secondary aliphatic amines of the present invention may berepresented by the formula RI in which R is an alkyl or alkenyl group of12 to 24 carbon atoms and R is an alkyl or alkenyl group of 12 to 24carbon atoms. The alkyl and alkenyl representations of R must contain atertiary carbon atom attached directly to the nitrogen atom, that is, inalpha position with respect to the nitrogen atom. These alkyl andalkenyl groups may also contain additional carbinyl carbon atoms andpreferably so. The alkyl and alkenyl representations of R must containat least one carbinyl carbon atom someplace in the group but it cannotbe the carbon atom alpha or beta to the nitrogen atom. It is preferredthat R be alkyl when R is alkenyl and that R" be alkyl when R isalkenyl. The preferred arrangement is for R to be alkyl and R' to bealkenyl. It is preferred that both R and R be highly branched.

The definition of R may be more fully understood from the followingformulas: (1) When R is an alkyl group of 12 to 24 carbon atoms, K maybe represented by A1 Aral a trialkylcarbinyl group, in which A A and Aare alkyl groups having a total of 11 to 23 carbon atoms and (2) When Ris an alkenyl group of 12 to 24 carbon atoms, R may be represented by AtAs-(J- a dialkylalkenylcarbinyl group, in which A A and A contain atotal of 11 to 23 carbon atoms and one of 2,870,207 Patented Jan. 20, 1959 n p 1C6- (1) When R' is an alkenyl group of 12 to 24 carbon atoms, Rmay be represented by a trialkylcarbinylbutenyl group, in which D D andD are alkyl groups containing a total of 7 to 19 carbon atoms and (2)When R is an alkyl group is contains from 12 to 24 carbon atoms at leastone of which is a carbinyl carbon. The term carbinyl is used in thedefinition of R in the same sense as it is used in the definition of Rexcept that the fourth valence of the carbinyl carbon in the definitionof R' is attached to a butenylene group or to an alkylene as will heunderstood from the foregoing discussion. The groups A A A A A A D D andD may contain carbinyl carbon atoms and it is desirable that, within anyone reactant, R amine or R halide to be more fully describedhereinafter, there be more than one carbinyl carbon atom.

Typical of the R representations are The present compounds are preparedby reacting an R amine with an R halide, such as chloride or bromide. Itis advantageous to use, when possible, an alkenyl halide, such as achloride or bromide, with an alkylamine, largely because the alkenylhalides used in this invention are somewhat more reactive than the alkylhalides.

Single compounds may be employed as reactants or mixtures of compoundsmay be used, as desired. Commercially available mixtures oftrialkylcarbinylamines are particularly useful in thise respect as Ramine reactants. Typical of these technical mixtures that may beemployed are those containing from l2'to 15 carbon atoms and from 18't024 carbon atoms in amine form. One of the trialkylcarbinylbutenylreactants that is of particular interest in the present instance is thatidentified as the 5,5,7,7-tetramethyl-2-octenyl group with a chlorine orbromine atom in the number one position.

The present secondary amines are formed by heating the reactants,already defined, at a reacting temperature in the range of about 75 to200 C., preferably 120' to 180 C. The reaction is equimolccular innature and yields greater than 75% and up to 95% or more areconsistently obtained.

During the course of the reaction hydrogen halide is evolved and it isdesirable to provide an alkaline hydrogen halide acceptor to remove thehydrogen halide, otherwise the reaction tends to become sluggish withyields appreciably reduced. There may be used in this respect solidsodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide,barium hydroxide, and the like, or an excess of the amine reactant. Ifsodium hydroxide or its equivalent is employed, it is advantageous tosupply a volatile, inert, organic solvent that forms an azeotrope withwater, such as toluene, xylene, or the like, in order that the waterformed by the neutralization reaction between the sodium hydroxide andthe evolved hydrogen halide may be azeotropically removed as thereaction progresses. It is not necessary to supply the azeotropicsolvent if an excess of the amine reactant is used as the hydrogenhalide acceptor since there is no water byproduct with which to cope. Itis advantageous to employ an excess of the amine reactant: as thehydrogen halide acceptor and in amounts such that substantially all ofthe evolved hydrogen halide is accepted. Since the present reactionoccurs on an equimolecular basis and since a molar quantity of the aminereactant is used to accept the hydrogen halide formed, it is preferredto employ the amine reactant in a two to one molar ratio with the halidereactant when an excess of the amine reactant is used as the hydrogenhalide acceptor.

If sodium hydroxide, potassium hydroxide or the like, is employed as thehydrogen halide acceptor, water is added to the reaction mixture, at theend of the reaction, to facilitate removal of the sodium or potassiumhalide salt formed as well as any excess alkali present. The water layeris easily separated from the organic layer containing the product. Theorganic layer is stripped preferably under reduced pressure to removethe solvent and any unused reactants. The product remains as the residueand may be distilled, if desired.

If an excess of the amine reactant is employed as the hydrogen halideacceptor, at the end of the reaction aqueous alkali is added to thereaction mixture and the resultant alkali halide salt formed is removedin the water layer along with any excess alkali. Any unused reactantsare stripped off preferably under reduced pressure leaving the productas the residue which may be distilled, if desired. The products areviscous liquids that have the same approximate color as the aminereactants.

The subject compounds are insoluble in water and soluble in kerosene andother petroleum hydrocarbons, such as benzene, xylene, and toluene,common organic solvents, and light and heavy mineral oils. The presentcompounds are useful in many hydro-metallurgical applications wherein akerosene or similar solution of one of the subject amines is agitated inan aqueous system containing the metal to be reclaimed or the metals tobe separated. The present secondary amines exhibit extremely lowemulsion tendencies and high extraction coefiicients in many of thesehydro-metallurgical systems. There may be separated fromhydro-metallurgical systems in the above manner niobium from tantalum,niobium from protactinium, zinc from cobalt, uranium from its salts, andothers, by employing the amines of this invention.

The subject amines are very useful for removing mineral acids, such ashydrochloric and sulfuric acids, from protein hydrolysates. These aminesmay also be employed to remove mineral acids such as hydrochloric andnitric acids from aqueous systems. For instance, employing a 0.1 Nsolution of the amine, whose preparation is shown in Example 1 tofollow, in kerosene in an aqueous system containing 0.094 N hydrochloricacid 93.4% of the acid is removed when a two-to-one amine-to-acid ratiois used and 95.5% is removed when a three-to-onc amine-toacid ratio isemployed. Using the same amine in the same concentration in kerosene inan aqueous system containing 0.1002 N nitric acid there is removed 97.5%of the acid when a two-to-one amine-to-acid ratio is used and 98.8% ofthe acid when a three-to-one amineto-acid ratio is employed. Similarresults are obtained by using the other amines of this invention. Theseamines are particularly useful in applications involving acid removalfrom aqueous systems because the amine salts formed are insoluble inwater and, therefore, are easily removed from the water component.Furthermore, these amines are readily recovered by regeneration withsodium hydroxide, sodium carbonate, ammonium hydroxide, or the like, andare available for reuse. Under like conditions, dilaurylamine and othersimilar a tines failed to produce the desired results. The dilaurylamineand other similar amine salts remained in the aqueous layer andappreciably aggravated the problem rather than solved it.

The secondary amines of this invention may also be employed as ashlessdetergents in lubricating oils, and, in amounts by weight in the rangeof about 0.0005 to 0.05%, are valuable as anti-sludging agents in fueloils, burner oils, diesel fuel oils, and other cracked and straight rundistillates normally tending to form sludge.

It is essential for the purposes of this invention that the presentsecondary amines contain the groups R and R as already defined in termsof molecular size and spatial configuration. Any appreciable deviationfrom the defined R and R' groups defeats the purposes of this invention.By strict adherence to the defined groups, there results a concomitanceof desirable properties that confers uniqueness on the compounds of thisinvention.

This application is a continuation-in-part of our application Serial No.530,391, filed August 24, 1955, now abandoned.

The compounds of the present invention may be more fully understood fromthe following examples that are presented by way of illustration and notby way of limitation. Parts by weights are used throughout.

Example I There is added to a flask equipped with a thermometer andstirrer 223 parts of l-chloro-5,5,7,7-tetramethyl-2- octene. A total of396 parts of a mixture of trialkylcarbinylamines containing 12 to 15carbon atoms, principally C H NH and C l-I NH, and having a neutralequivalent of 191, is added over a period of one hour, during which timethe temperature is maintained at to C. At the completion of the additionof the amine reactant, the temperature is raised to 180 C. for one hour.The reaction mixture is then neutralized by the addition of 40 parts ofsodium hydroxide dissolved in 200 parts of water and heating theresultant mixture to 80 C. for one-half hour. The mixture is allowed tocool and separate into layers. The lower aqueous layer is discarded andthe upper organic layer is stripped under reduced pressure using a smallportion of benzene to assure the removal of all of the water. Thestripped mixture is filtered hot and then distilled under reducedpressure. The product distills at 148 to C. at 0.5 to 2.5 mm. ofpressure. The product corresponds to a mix ture of secondary amines inwhich the 5,5,7,7-tetramethyl- Z-octenyl group is attached to the aminonitrogen of the trialkylcarbinylamine reactants.

In a similar way, a secondary amine of this invention is prepared byreacting l-bromo-5,5,7,7-tetramethyl-2- octene with a mixture oftrialkylcarbinylamine containing 18 to 24 carbon atoms, principally C HNI-I, and C H NH and having a neutral equivalent of 320.

Example 2 There are introduced into a reaction vessel 202.5 parts ofl-chloro-S,5,7,7-tetramethy1-2-octene and 706 parts of atrialkylcarbinylamine containing 24 carbon atoms. The reaction mixtureis heated at 160 to 175 C. for two and a half hours. There is then added56 parts of potassium hydroxide dissolved in 200 parts of water. Theresultant mixture is heated to 75 C. and stirred for 40 minutes. Themixture is allowed to cool and separate into layers. The lower aqueouslayer is discarded and the upper organic layer is stripped under reducedpressure. The stripped mixture is filtered hot leaving the product asthe filtrate. The product corersponds to the secondary amine of thisinvention in which the 5,5,7,7-tetramethyl-2- octenyl group is attachedto the amino nitrogen of the trialkylcarbinylamine reactant. The productmay be named N-(5,5,7,7-tetramethyl-2-octeny1)-N-tetracosanylamine.

Example 3 There are brought together in a reaction vessel 286.5 parts ofa trialkylcarbinylbutenyl chloride containing 18 carbon atoms and 702parts of tricosylcarbinylamine. The mixture is heated for three hours at170 to 175 C. and then 40 parts of sodium hydroxide dissolved in 175parts of water is added. The mixture is stirred for 30 minutes at 75 C.and isthen allowed to cool and separate into layers. The product isobtained as the residue from the upper organic layer after the layer hasbeen stripped under reduced pressure. The product corresponds to thesecondary amine of this invention which may be namedN-octadecenyl-N-tetracosylamine.

There is prepared in like manner the secondary amine of this inventionnamed N-odecyl-N-eicosylamine by reacting a trialkylcarbinylaminecontaining 12 carbon atoms with an eicosyl bromide containing a carbinylatom further than alpha or beta away from the bromine atom.

In a similar way, there is made the secondary amine of this inventionnamed N-tetracosyl-N-tetracosenylamine by reacting atrialkylcarbinylamine containing 24 carbon atoms with tetracosenylchloride containing a carbinyl carbon atom further than alpha or betaaway from the chlorine atom.

Example 4 There are added to a reaction vessel 213 parts of atrialkylcarbinylamine containing 14 carbon atoms, 40 parts of sodiumhydroxide, and 50 parts of xylene. There is slowly added over a periodof 40 minutes 286.5 parts of trialkylcarbinylbutenyl chloride having 18carbon atoms while the temperature is maintained at 150 C. The reactionmixture is heated at 165 C. to 170 C. for four hours during which timewater is distilled from the reaction vessel. The mixture is cooled,filtered, washed with water, and allowed to separate into layers. Theorganic layer is stripped leaving the product as the residue. Theproduct corresponds to a secondary amine of this invention and may benamed N-tetradecyl-N-octadecenylamine.

There is similarly prepared a secondary amine of this invention, whichmay be named N-hexadencyl-N-docosylamine, by reacting atrialkylcarbinylamine having 22 carbon atoms with atrialkylcarbinylbutenyl chloride having 16 carbon atoms.

We claim:

.1. As a new composition of matter, the secondary amine having theformula NII in which R is a member from the class consisting of alkyland alkenyl groups of 12 to 24 carbon atoms and R is a member from theclass consisting of alkyl and alkenyl groups of 12 to 24 carbon atoms.said R group having a carbinyl carbon atom attached directly to theamino nitrogen atom and said R group having at least one carbinyl carbonatom no one of which is closer than gamma with respect to the aminonitrogen atom.

. .6 2. As a new composition of matter, the secondary amine having theformula in which R is an alkenyl group of 12 to 24 carbon atomscontaining at least one carbinyl carbon atom no one of which is closerthan gamma with respect to the amino nitrogen atom and R is an alkylgroup of 12 to 24 carbon atoms containing a carbinyl carbon atomattached directly to the amino nitrogen atom.

3. As a new composition of matter, the secondary amine having theformula in which R is a trialkylcarbinylbutenyl group of 12 to 24 carbonatoms and R is a trialkylcarbinyl group of 18 to 24 carbon atoms.

6. As a new composition of matter, the secondary amine having theformula in which R is the 5,5,7,7-tetramethyl-2-octenyl group and R [S atrialkylcarbinyl group of 18 to 24 carbon atoms.

8. A method for the preparation of a secondary amine having the formulain which R is a member from the class consisting of alkyl and alkenylgroups of 12 to 24 carbon atoms and R is a member from the classconsisting of alkyl and alkenyl groups of 12 to 24 carbon atoms, said Rgroup having a carbinyl carbon atom attached directly to the aminonitrogen atom and said R group having at least one carbinyl carbon atomno one of which is closer than gamma with respect to the amino nitrogenatom, which comprises heating in the presence of a hydrogen halideacceptor and at a reacting temperature in the range of about 75 to 200C. and R amine with an R halide, said halide 7 portion of the R reactanthaving an atomic weight of about 35.5 to 80.

9. A method for the preparation of a secondary amine having the formula\NH' u in which R is a member from the class consisting of alkyl andalkenyl groups of 12 to 24 carbon atoms and R is a member from the classconsisting of alkyl and alkenyl groups of 12 to 24 carbon atoms, said Rgroup having a carbinyl carbon atom attached directly to the aminonitrogen atom and said R group having at least one carbinyl carbon atomno one of which is closer than gamma with respect to the amino nitrogenatom, which comprises heating in the presence of an alkaline hydrogenhalide acceptor from the class consisting of solid alkali metal andalkaline earth oxides and hydroxides in the presence of a volatile inertorganic solvent that forms an azeotrope with water, and at a reactingtemperature in the range of about 75 to 200 C. an R amine with an Rhalide, said halide portion of the R reactant having an atomic weight ofabout 35.5 to 80.

10. A method for the preparation of a secondary amine having the formulain which R is a member from the class consisting of alkyl and alkenylgroups of 12 to 24 carbon atoms and R is a member from the classconsisting of alkyl and alkenyl groups of 12 to 24 carbon atoms, said Rgroup having a carbinyl carbon atom attached directly to the aminonitrogen atom and said R group having at least one carbinyl carbon atomno one of which is closer than gamma with respect to the amino nitrogenatom, which comprises heating at a reacting temperature in the range ofabout 75 to 200 C. an R amine with an R halide, said R amine beingpresent in amounts approximately twice that of said R halide, saidhalide portion of the R reactant having an atomic weight of about 35.5to 80.

II. A method for the preparation of a secondary amine having the formulain which R is an alkenyl group of 12 to 24 carbon atoms containing atleast one carbinyl carbon atom no one of which is closer than gamma tothe amino nitrogen atom and R is an alkyl group of 12 to 24 carbon atomscontaining a carbinyl carbon atom attached directly to the aminonitrogen atom. which comprises heating at a reacting temperature in therange of about 75 to 200 C. an R halide, in which the halide portion hasan atomic weight of about 35.5 to 80, with an R amine.

12. A method for the preparation of a secondary amine having the formulain which R is a trialkylcarbinyl group of 12 to 24 carbon atoms and R isa trialkylcarbinylbutenyl group of 12 to 24 carbon atoms, whichcomprises heating at a reacting temperature of about to 200 C. an Rhalide, in which the halide portion has an atomic weight of about 35.5to 80, with an R amine, said amine being present in amounts ofapproximately twice that of said halide.

13. A method for the preparation of a secondary amine having the formulain which R is a trialkylcarbinylbutenyl group of 12 to 24 carbon atomsand R is a trialkylcarbinyl group of 12 to 15 carbon atoms, whichcomprises heating at a reacting temperature of about 75 to 200 C. an R'halide, in which the halide portion has an atomic weight of about 35.5to 80, with an R amine, said amine being present in amountsapproximately twice that of said halide.

14. A method for the preparation of a secondary amine having the formulain which R is a trialkylcarbinylbutenyl group of 12 to 24 carbon atomsand R is a trialkylcarbinyl group of 18 to 24 carbon atoms, whichcomprises heating at a reacting temperature of about 75 to 200 C. an Rhalide, in which the halide portion has an atomic weight of about 35.5to 80, with an R amine, said amine being present in amountsapproximately twice that of said halide.

15. A method for the preparation of a secondary amine having the formulain which R is the 5,5,7,7-tetramethyl-2-octcnyl group and R is atrialkylcarbinyl group of 12 to 15 carbon atoms, which comprises heatingat a reacting temperature of about 75 to 200 C. an R halide, in whichthe halide portion has an atomic weight of about 35.5 to 80, with an Ramine, said amine being present in amounts approximately twice that ofsaid halide.

16. A method for the preparation of a secondary amine having the formulain which R is the 5,5,7,7-tetramethyl-2-0ctenyl group and R is atrialkylcarbinyl group of 18 to 24 carbon atoms, which comprises heatingat a reacting temperature of about 75 to 200 C. and R halide, in whichthe halide portion has an atomic weight of about 35.5 to 80, with an Ramine, said amine being present in amounts approximately twice that ofsaid halide.

No references cited.

1. AS A NEW COMPOSITION OF MATTER, THE SECONDARY AMINE HAVING THEFORMULA